Coloring composition comprising at least one pigment and at least one electrophilic cyanoacrylate monomer

ABSTRACT

The present disclosure relates to a dyeing composition comprising, in an appropriate dyeing medium, at least one pigment and at least one electrophilic cyanoacrylate monomer of formula (I)  
                 
in which R is chosen from alkyl radicals and alkoxyalkyl radicals. Dyeing kits comprising said compositions and processes using same are also disclosed.

This application claims benefit of U.S. Provisional Application No.60/638,110 filed Dec. 23, 2004, the contents of which are incorporatedherein by reference. This application also claims benefit of priorityunder 35 U.S.C. § 119 to French Patent Application No. 04 10800, filedOct. 13, 2004, the contents of which are also incorporated by reference.

The present disclosure relates to a composition for coloring/dyeingkeratin materials, for instance keratin fibers such as the hair,comprising at least one pigment and at least one particularelectrophilic monomer, and a process for dyeing keratin materials usingthis composition.

Within the field of coloring keratin fibers it is already known to colorkeratin fibers by a variety of techniques, starting from direct dyes orpigments, for non-permanent colorations, or from dye precursors, forpermanent colorations.

Non-permanent coloration or direct coloration involves dyeing thekeratin fibers with dyeing compositions containing direct dyes. Thesedyes are colored, and coloring molecules which have an affinity for thekeratin fibers. They are applied to the keratin fibers for a timerequired for the desired coloration to be obtained, then rinsed off.

The conventional dyes which are used include, for example, dyes of thenitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine,azine or triarylmethane type or natural dyes.

Some of these dyes can be used under lightening conditions, allowingcolorations to be obtained which are visible on dark hair.

It is also known to dye keratin fibers permanently by oxidationcoloring. This coloring technique involves applying to the keratinfibers a composition containing dye precursors such as oxidation basesand couplers. These precursors, under the action of an oxidant, willform at least one colored species in the hair.

The variety of molecules employed as oxidation bases and couplers canmake it possible to obtain a rich palette of colors, and the colorationsresulting from them can be permanent, powerful, and/or resistant toexternal agents, in particular to light, inclement weather, washing,perspiration, and rubbing.

In order to be visible on dark hair, the colorations resulting fromthese two coloring techniques require a prior or simultaneous bleachingof the keratin fibers. This bleaching step, carried out with an oxidantsuch as hydrogen peroxide or persalts, can entail a not inconsiderableamount of degradatiori of the keratin fibers, which may impair theircosmetic properties. The hair then has a tendency to become rough, lesseasy to disentangle, and/or more fragile.

Another method of coloring keratin fibers involves using pigments. Ineffect, the use of a pigment at the surface of the keratin fibers makesit possible, generally speaking, to obtain colorations which are visibleon dark hair, since the surface pigment masks the natural color of thefiber. The use of pigments for coloring keratin fibers is described, forexample, in French Patent Application Publication No. FR 2 741 530,which recommends the use, for the coloring of the keratin fibers, of acomposition comprising at least one dispersion of particles offilm-forming polymer comprising at least one acid functional group, andat least one pigment dispersed in the continuous phase of saiddispersion.

The coloration obtained by this mode of coloring can have the drawbackof having a low level of resistance to shampooing.

French Patent Application Publication No. FR 2 833 489 discloses hairtreatment compositions on the basis of compositions comprisingelectrophilic monomers. A composition of this kind can make it possibleto obtain hair which is extremely well coated and not greasy.

The present disclosure, therefore, relates to new compositions forcoloring or dyeing keratin materials, for instance keratin fibers suchas the hair, which make it possible to obtain colorations which arevisible on dark hair, without the need to lighten or bleach the fibers,and/or which may exhibit good resistance to shampooing.

Thus, in one embodiment, the present disclosure relates to a process fordyeing keratin materials such as keratin fibers comprising applying tothe fibers a dyeing composition comprising, in a suitable dyeing medium,at least one pigment and at least one electrophilic cyanoacrylatemonomer of formula (I)

in which R is chosen from alkyl radicals and alkoxyalkyl radicals.

The present disclosure also relates to a composition comprising, in asuitable dyeing medium, at least one pigment in an amount greater than5% (w/w) by weight and at least one cyanoacrylate electrophilic monomerof formula (I).

The process in accordance with the present disclosure can make itpossible to obtain a visible coloration on a dark keratin material. Forexample, in the case of dark keratin fibers, a highly visible colorationis obtained with no need to lighten or bleach the keratin fibers andhence it is possible to obtain a visible coloration on a dark keratinmaterial without risking physical degradation of the keratin fibers.Moreover, this coloration exhibits good resistance to the variousaggressive influences to which the hair may be subjected, such asshampooing, rubbing, light, inclement weather, perspiration, andpermanent reshaping (“perming”). In at least one embodiment, thecoloration shows good resistance to shampooing.

Given the variety of pigments which can be used in the composition ofthe present disclosure, it is possible to obtain colorations in varied,powerful and aesthetic shades, which can also be chromatic.

The present disclosure additionally relates to a kit comprisingcompositions comprising at least one pigment and at least oneelectrophilic cyanoacrylate monomer of formula (I).

As used herein, a “pigment” is understood to mean any organic and/orinorganic entity whose solubility in water is less than 0.01% at 20° C.,for instance less than 0.0001%, and which exhibits absorption at awavelength ranging from 350 nm to 700 nm, such as absorption with onemaximum.

The pigments that can be useful in the present disclosure are selectedfrom any organic and/or inorganic pigments known in the art, such asthose described in the Kirk-Othmer encyclopaedia of chemical technologyand in the Ullmann encyclopaedia of industrial chemistry.

The at least one pigment may be present in pigment paste or powder form.

The at least one pigment in accordance with the present disclosure may,for example, be chosen from white and/or colored pigments, lakes,special-effect pigments such as nacres or flakes, and mixtures thereof.

Non-limiting examples of white or colored inorganic pigments includetitanium dioxide, with or without surface treatment, oxides of zirconiumor of cerium, oxides of iron or of chromium, manganese violet,ultramarine blue, chromium hydrate and Prussian Blue. For example, thefollowing inorganic pigments may be used: Ta₂O₅, Ti₃O₅, Ti₂O₃, TiO, ZrO₂mixed with TiO₂, ZrO₂, Nb₂O₅, CeO₂, ZnS.

Non-limiting examples of white or colored organic pigments includenitroso, nitro, azo, xanthene, quinoline, anthraquinone andphthalocyanine compounds, metal complex compounds, and isoindolinone,isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole,thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

For instance, by way of non-limiting example, the white or coloredorganic pigments may be chosen from carmine, carbon black, anilineblack, azo yellow, quinacridone, phthalocyanine blue, sorghum red, theblue pigments codified in the Colour Index under references CI 42090,69800, 69825, 73000, 74100 and 74160, the yellow pigments codified inthe Colour Index under references CI 11680, 11710, 15985, 19140, 20040,21100, 21108, 47000 and 47005, the green pigments codified in the ColourIndex under references CI 61565, 61570, 74260, the orange pigmentscodified in the Colour Index under references CI 11725, 15510, 45370 and71105, the red pigments codified in the Colour Index under references CI12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630,15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360,73915 and 75470, pigments obtained by oxidative polymerization of indoleor phenolic derivatives as described in French Patent No. FR 2 679 771.

It is also possible to use pigment pastes of organic pigment, such asthe products sold by the company Hoechst under the name: Jaune CosmenylIOG: Pigment Yellow 3 (CI 11710); Jaune Cosmenyl G: Pigment Yellow 1 (CI11680); Orange Cosmenyl GR: Pigment Orange 43 (CI 71105); Rouge CosmenylR: Pigment Red 4 (CI 12085); Carmin Cosmenyl FB: Pigment Red 5 (CI12490); Violet Cosmenyl RL: Pigment Violet 23 (CI 51319); Bleu CosmenylA2R: Pigment Blue 15.1 (CI 74160); Vert Cosmenyl GG: Pigment Green 7(CI74260); Noir Cosmenyl R: Pigment Black 7 (CI 77266).

The pigments in accordance with the present disclosure may also be inthe form of composite pigments as described in European Patent No. EP 1184 426. These composite pigments may be composed of, for example,particles comprising an inorganic core, at least one binder attachingthe organic pigments on the core, and at least one organic pigment atleast partly covering the core.

As used herein, the term “lakes” is understood to mean dyes adsorbed oninsoluble particles, the resultant assembly remaining insoluble duringuse. The inorganic substrates on which the dyes are adsorbed are, forexample, alumina, silica, calcium sodium borosilicate or calciumaluminium borosilicate, and aluminium. Among the organic dyes,non-limiting mention may be made of cochineal carmine.

Non-limiting examples of lakes include the products known under thefollowing names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D& C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45430), D & C Red 7 (CI 15 850:1), D & C Red 4 (CI 15 510), D & C Red 33(CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D &C Green (CI 61 570), D & C Yellow 1 0 (CI 77 002), D & C Green 3 (CI 42053) and D & C Blue 1 (CI 42 090).

As used herein, the term “special-effect pigments” is understood to meanpigments which create, generally speaking, a colored appearance(characterized by a certain shade, a certain liveliness and a certainlightness) which is not uniform and which changes as a function of theconditions of observation (e.g., light, temperature, viewing angles,etc.). They are consequently in contrast to white or colored pigments,which provide a conventional opaque, semi-transparent or transparent,uniform hue.

Non-limiting examples of special-effect pigments include white nacreouspigments such as mica coated with titanium or with bismuth oxychloride,colored nacreous pigments such as mica coated with titanium and ironoxides, mica coated with titanium, and, for instance, Prussian Blue orchromium oxide, mica coated with titanium and an organic pigment asdefined above, and also nacreous pigments based on bismuth oxychloride.Nacreous pigments include the nacres Cellini, sold by Engelhard(mica-TiO₂-lake), Prestige, sold by Eckart (mica-TiO₂) and Colorona,sold by Merck (mica-TiO₂—Fe₂O₃).

Non-limiting mention may also be made of interference-effect pigmentsnot attached to a substrate, such as liquid crystals (Helicones HC fromWacker), holographic interference flakes (Geometric Pigments or Spectraf/x from Spectratek). Special-effect pigments can also comprisefluorescent pigments, whether they be daylight-fluorescent substances orsubstances which produce ultraviolet fluorescence, phosphorescentpigments, photochromic pigments, thermochromic pigments, and quantumdots, sold for example by the company Quantum Dots Corporation.

The quantum dots are luminescent semi-conductive nanoparticles capableof emitting, under excitation by light, radiation having a wavelengthranging from 400 nm to 700 nm. These nanoparticles are known from theliterature. For instance, they may be manufactured by the processesdescribed, for example, in U.S. Pat. Nos. 6,225,198 or 5,990,479, in thepublications cited therein, and also in the following publications:Dabboussi B. O. et al “(CdSe)ZnS Core-shell Quantum Dots: Synthesis andCharacterisation of a Size Series of Highly LuminescentNanocrystallites” Journal of Physical Chemistry B, Vol. 101, 1997, pp9463-9475, and Peng, Xiaogang et al, “Epitaxial Growth of HighlyLuminescent CdSe/CdS core/shell nanocrystals with Photostability andElectronic Accessibility,” Journal of the American Chemical Society,Vol. 119, No. 30, pp 7019-7029.

The variety of pigments which can be used in the present disclosureallows a rich palette of colors to be obtained, and also certain opticaleffects, such as metallic and interference effects.

According to one embodiment of the present disclosure, the at least onepigment is chosen from colored pigments. As used herein, the term“colored pigments” is understood to mean pigments other than the whitepigments.

The size of the at least one pigment which can be used in the context ofthe present disclosure can range from 10 nm to 200 μm, for instance,from 20 nm to 80 μm, and such as from 30 nm to 50 μm.

The at least one pigment can be present in the composition in accordancewith the present disclosure, in an amount for each pigment, ranging from0.05% to 50% by weight, relative to the total weight of the composition,such as ranging from 0.1% to 35% by weight, relative to the total weightof the composition.

In the context of the present disclosure, the alkyl or alkoxyalkylradicals may be linear or branched, and may be cyclic.

Non-limiting examples of cyanoacrylate monomers of formula (I) includethe electrophilic monomers ethyl 2-cyanoacrylate, methyl2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate,tert-butyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, isobutyl2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate,hexyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2-methoxyethyl2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl2-cyanoacrylate, n-octyl 2-cyanoacrylate and isoamyl cyanoacrylate.

According to one embodiment of the present disclosure, the at least oneelectrophilic cyanoacrylate monomer of formula (I) is chosen from thosecomprising alkyl or alkoxyalkyl radicals R of 1 to 10 carbon atoms, suchas of 6 to 10 carbon atoms.

According to another embodiment of the present disclosure, the at leastone electrophilic cyanoacrylate monomer is chosen fromalkyl(C₆-C₁₀)cyanoacrylates. According to still another embodiment, theat least one electrophilic cyanoacrylate monomer is chosen from octyl2-cyanoacrylate monomers, linear or branched.

In yet another embodiment of the present disclosure, the at least oneelectrophilic cyanoacrylate monomer is chosen from those of thefollowing formula and mixtures thereof:

in which: Z is chosen from —(CH₂)₇—CH₃, CH(CH₃)—(CH₂)₅—CH₃,CH₂—CH(C₂H₅)—(CH₂)₃—CH₃, (CH₂)₅—CH(CH₃)—CH₃, and (CH₂)₄—CH(C₂H₅)—CH₃monomers.

The at least one electrophilic cyanoacrylate monomer used in thecomposition of the present disclosure may be attached covalently tosupports such as polymers, oligomers or dendrimers. The polymer oroligomer may have a linear, branched, comb or block structure. Thedistribution of the monomers of the present disclosure over thepolymeric, oligomeric or dendritic structure may be random, terminal orblockwise.

In the composition of the present disclosure, the at least oneelectrophilic cyanoacrylate monomer can be present in an amount rangingfrom 0.1% to 80% by weight, relative to the total weight of thecomposition, such as from 1% and 50%.

In the context of the present disclosure, the electrophiliccyanoacrylate monomers of formula (I) are monomers capable of undergoinganionic polymerization in the presence of an nucleophile. As usedherein, the term “anionic polymerization” is understood to mean themechanism defined in the work “Advanced Organic Chemistry,” thirdedition, by Jerry March, pages 151 to 161. The nucleophiles capable ofinitiating the anionic polymerization are systems which are known per seand which are capable of generating a carbanion on contact with anucleophile, such as the hydroxide ions present in water at neutral pH.As used herein, the term “carbanions” is understood to mean the chemicalspecies defined in “Advanced Organic Chemistry,” third edition, by JerryMarch, page 141.

The nucleophiles may be applied independently of the composition of thepresent disclosure. They may also be added to the composition of thepresent disclosure at the time of use.

The nucleophile is a molecular compound, an oligomer, a dendrimer or apolymer which possesses nucleophilic functional groups. Withoutlimitation, nucleophilic functional groups that may be mentioned includethe following functional groups: R₂N⁻, NH₂ ⁻, Ph₃C⁻, R₃C⁻, PhNH⁻,pyridine, ArS⁻, R—C^(≡)C—, RS⁻, SH⁻, RO⁻, R₂NH, ArO⁻, N₃ ⁻, OH⁻, ArNH₂,NH₃, I⁻, Br⁻, Cl⁻, RCOO⁻, SCN⁻, ROH, RSH, NCO⁻, CN⁻, NO₃, ClO₄ ⁻ andH₂O, wherein Ph is a phenyl group; Ar is an aryl group, and R is aC₁-C₁₀ alkyl group.

The at least one electrophilic cyanoacrylate monomer of formula (I)according to the present disclosure may be synthesized by the knownmethods described in the art. For example, the electrophiliccyanoacrylate monomers may be synthesized according to the teaching ofU.S. Pat. Nos. 3,527,224, 3,591,767, 3,667,472, 3,995,641, 4,035,334 and4,650,826.

The suitable dyeing medium used in the composition of the presentdisclosure can be, for example, a non-hygroscopic anhydrous medium. Asused herein, the term “anhydrous medium” is understood to mean a mediumcomprising less than 1% of water by weight.

According to one embodiment the dyeing medium of the composition of thepresent disclosure can be chosen, for example, from:

-   -   aromatic alcohols such as benzyl alcohol;    -   fatty alcohols;    -   modified and non-modified polyols, such as glycerol, glycol,        propylene glycol, dipropylene glycol, butylene glycol and butyl        diglycol;    -   volatile and non-volatile silicones, such as cyclopentasiloxane,        cyclohexasiloxane, polydimethylsiloxanes with or without        modification by phenyl and/or siloxy and/or silanol and/or amine        and/or imine and/or fluoroalkyl and/or carboxyl and/or betaine        and/or quaternary ammonium and/or etc. functions;    -   mineral oils, organic oils, vegetable oils;    -   oxyethylenated and non-oxyethylenated waxes, paraffins and        alkanes, such as C₅ to C₁₀ alkanes;    -   fatty acids, fatty amides, fatty esters, and for instance fatty        alcohol salicylates or benzoates.

According to one embodiment of the present disclosure, the medium iscomposed of a silicone, such as polydimethylsiloxanes and modifiedpolydimethylsiloxanes.

The dyeing medium of the composition of the present disclosure may alsobe in the form of an emulsion and/or may be encapsulated, the at leastone electrophilic monomer being maintained within an anhydrous mediumuntil the moment of use. When the dyeing medium is an emulsion, thisemulsion can comprise, for example, a disperse or continuous phase whichmay be composed of water, C₁-C₄ aliphatic alcohols or mixtures thereof,and an anhydrous organic phase comprising the at least one monomer. Inthe case of capsules or microcapsules, the capsules may comprise the atleast one monomer in an anhydrous medium, and may themselves bedispersed in an anhydrous medium as defined above, water, C₁-C₄aliphatic alcohols or mixtures thereof.

The organic compounds can be chosen from, for example, compounds whichare liquid at a temperature of 25° C. and under 105 Pa (760 mmHg).

It is also possible to introduce at least one polymerization inhibitorinto the composition of the present disclosure, such as free-radicaland/or anionic polymerization inhibitors, in order to increase thestability of the composition over time. Without limitation, mention maybe made of the following polymerization inhibitors: sulphur dioxide,nitric oxide, organic acids such as a sulphonic acid or phosphoric acid,acetic acid, lactone, boron trifluoride, hydroquinone and itsderivatives such as hydroquinone monoethyl ether,tert-butylhydroquinone, benzoquinone and its derivatives such asduroquinone, catechol and its derivatives such as tert-butylcatechol andmethoxycatechol, anisole and its derivatives such as methoxyanisole orhydroxyanisole, pyrogallol and its derivatives, p-methoxyphenol,hydroxybutyltoluene, alkyl sulphates, alkyl sulphites, alkyl sulphones,alkyl sulphoxides, alkyl sulphides, mercaptans, and mixtures thereof.The alkyl groups can be, for instance, chosen from groups having from 1to 6 carbon atoms.

The at least one inhibitor can be present in the composition of thepresent disclosure in an amount ranging from 10 ppm to 10% by weight,such as from 50 ppm to 5% by weight, relative to the total weight of thecomposition.

The composition of the present disclosure may also comprise at least onepolymer which does not exhibit any reactivity with the at least oneelectrophilic cyanoacrylate monomer, and which is capable of increasingthe viscosity of the composition. The increase in viscosity can make itpossible to reduce the polymerization rate of the cyanoacrylatemonomers. In order to do this it is possible to add to the compositionof the present disclosure, non-exhaustively, polymethyl methacrylate(PMMA) or else cyanoacrylate-based copolymers of the kind described inU.S. Pat. No. 6,224,622.

The composition of the present disclosure may also comprise at least onefiller. As used herein, the term “filler” is understood to mean, withoutlimitation, colorless or white, mineral or synthetic, lamellar ornon-lamellar particles. The at least one filler may be present in anamount ranging from 0% to 48% by weight, relative to the total weight ofthe composition, for instance from 0.01% to 30% by weight, and such asfrom 0.02% to 20% by weight. Non-limiting mention may be made, forexample, of talc, zinc stearate, mica, kaolin, polyamide (Nylon®)powders (ORGASOL from Atochem), polyethylene powders,tetrafluoroethylene polymer powders (Teflon®), starch, boron nitride,polymeric microspheres such as those of polyvinylidenechloride/acrylonitrile, for instance EXPANCEL (Nobel Industries), and ofacrylic acid copolymers (Polytrap® from the company Dow Corning) andsilicone resin microbeads (Tospearls® from Toshiba, for example), andelastomeric organopolysiloxanes.

The composition may also comprise at least one conventional cosmeticadjuvant. Without limitation, mention may be made of reductants,oxidants, fats, silicones, thickeners, softeners, antifoams,moisturizers, emollients, alkalifiers, elastomers, plasticizers,sunscreens, clays, colloidal minerals, perfumes, peptizers,preservatives, anionic, cationic, amphoteric, zwitterionic or nonionicsurfactants, fixative or non-fixative polymers, conditioning polymers,proteins, and vitamins.

The composition disclosed herein may also comprise at least one metalpowder or particle, such as particles or powders of aluminium and ofcopper.

These compositions may be present in a variety of forms, such aslotions, sprays and mousses, and may be applied as a shampoo orconditioner.

In the case of sprays, the composition of the present disclosure maycomprise at least one propellant. The propellant is composed of thecompressed or liquefied gases which are commonly employed for preparingaerosol compositions. For example, the at least one propellant can bechosen from air, carbon dioxide, compressed nitrogen or else a solublegas such as dimethyl ether, hydrocarbons which are halogenated (e.g.,fluorinated) or non-halogenated, and mixtures thereof.

The present disclosure also relates to a process comprising applying thecomposition of the present disclosure to keratin materials, for instancekeratin fibers such as the hair, in the presence of at least onenucleophile.

According to one embodiment of the process of the present disclosure,the at least one nucleophile capable of initiating the polymerization ofthe at least one cyanoacrylate monomer may be applied to the keratinfibers beforehand. The at least one nucleophile may be used in pureform, in solution, or in the form of an emulsion, or may beencapsulated. It may also be added to the anhydrous composition at thetime of use, just before application to the keratin fibers.

By way of non-limiting example, the at least one nucleophile can bewater. This water may be provided, for example, by prior wetting of thekeratin fibers. It may also be added directly to the composition beforeapplication.

According to one embodiment, it is possible to modify the polymerizationkinetics by wetting the fibers beforehand by means of an aqueoussolution whose pH has been adjusted using a base, an acid or anacid/base mixture. The acid and/or the base may be inorganic or organic.

According to another embodiment, the process of the present disclosuremay be carried out in a number of steps comprising applying acomposition containing at least one pigment to the fibers, and thenapplying a composition comprising the at least one electrophiliccyanoacrylate monomer of formula (I), wherein the at least onenucleophile is present in the composition comprising the pigment or in aseparate composition. According to this embodiment, the compositioncomprising the at least one pigment can be, for example, an aqueoussolution of pigments, which allows the fiber to be wetted and thepolymerization to be initiated when the at least one electrophiliccyanoacrylate monomer is applied.

According to the process of the present disclosure, another embodimentcomprises either applying the at least one electrophilic cyanoacrylatemonomer and the at least one pigment from a single composition, orapplying the at least one pigment in a first phase and then the at leastone electrophilic cyanoacrylate monomer.

The process of the present disclosure may include additional,intermediate or final, steps, such as the application of a cosmeticproduct, a rinsing step and/or a drying step. Drying may be carried outunder a hood, with a hairdryer and/or with a smoothing iron. Forexample, the application of the compositions in accordance with thepresent disclosure may be followed by a rinsing operation.

It is also possible to carry out multiple applications of thecomposition of the present disclosure, so as to obtain a superpositionof layers, to achieve specific properties of the deposit in terms ofchemical nature, mechanical strength, thickness, appearance and/or feel.

In order to improve, among other things, the adhesion of thepoly(cyanoacrylate) formed in situ, the fiber may be pretreated with anytypes of polymer.

In order to modify the anionic polymerization kinetics it is alsopossible to enhance the nucleophilicity of the fiber by chemicalconversion of the keratin fibers. By way of example, non-limitingmention may be made of the reduction of the disulfide bridges, of whichthe keratin is partly composed, to thiols before the composition of thepresent disclosure is applied. Non-exhaustively, mention may be made, asreductants of the disulfide bridges of which the keratin is partlycomposed, of the following compounds: anhydrous sodium thiosulphate,powdered sodium metabisulphite, thiourea, ammonium sulphite,thioglycolic acid, thiolactic acid, ammonium thiolactate, glycerolmonothioglycolate, ammonium thioglycolate, thioglycerol,2,5-dihydroxybenzoic acid, diammonium dithioglycolate, strontiumthioglycolate, calcium thioglycolate, zinc formaldehyde-sulphoxylate,isooctyl thioglycolate, dl-cysteine and monoethanolamine thioglycolate.

Application of the composition of the present disclosure may also bepreceded by a hair treatment, such as a direct or oxidation coloringoperation.

According to the present disclosure, the at least one electrophiliccyanoacrylate monomer can be chosen from, for example, monomers capableof undergoing polymerization on the keratin fibers under cosmeticallyacceptable conditions. For instance, the polymerization of the at leastone electrophilic cyanoacrylate monomer can take place at a temperatureless than or equal to 80° C., such as ranging from 10° C. to 80° C., forexample ranging from 20° C. to 80° C., which does not prevent theapplication being finished by drying under a hood, blow-drying or thepassage of a flat iron or curling tongs.

The present disclosure additionally relates to a coloring kit comprisingat least one first composition, which comprises at least one pigment,and at least one second composition, which comprises at least oneelectrophilic cyanoacrylate monomer of formula (I) and, optionally, atleast one third composition, which comprises at least one nucleophile.According to this embodiment, the at least one composition comprisingthe at least one pigment is an aqueous composition and the at least onecomposition comprising the at least one electrophilic cyanoacrylatemonomer is an anhydrous composition.

According to another embodiment, the kit comprises at least one first,anhydrous composition, which comprises at one pigment and at least oneelectrophilic cyanoacrylate monomer, and at least one secondcomposition, which comprises at least one nucleophile.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be understood asbeing modified in all instances by the term “about.” Accordingly, unlessindicated to the contrary, the numerical parameters set forth in thefollowing specification and attached claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent disclosure. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should be construed in light of thenumber of significant digits and ordinary rounding approaches.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

The non-limiting examples below make it possible to illustrate thepresent disclosure without, however, limiting its scope.

EXAMPLES

Tests were conducted using the following compounds:

Monomer: 2-octyl 2-cyanacrylate stabilized with 1% of phosphoric acid,known under the name Rite Lok CON895, sold by the Chemence company

Pigment 1: Brown iron oxide CI 77491, sold by LCW,

Pigment 2: Titanium oxide/mica nacre with gold interference glints, soldby Eckart under the name Prestige Gold.

Coloring/Dyeing medium:

50%poly(alpha-omega-dihydroxydimethylsiloxane)/cyclopentadimethylsiloxane(14.7/85.3) mixture, sold by Dow Corning under the name DC 1501 Fluid

50% cyclopentadimethylsiloxane sold by Dow Corning under the name DC 245Fluid.

Example 1

An aqueous composition was prepared with 10% by weight of pigment 1. 0.5g of this aqueous solution was applied to 1 g of a lock of clean, drynatural hair with a tone height of 4, corresponding to a naturalchestnut shade in accordance with the classification of natural shadesthat is described in “Science des Traitements Capillaires,” by C. Zviak,Ed. Masson 1988, p. 278.

The lock was subsequently dried under a hood, then wetted with 0.5 g ofwater. Applied to this wetted lock was 0.5 g of a composition comprisingthe above-described coloring medium and 10% by weight of thecyanoacrylate monomer.

After an exposure time of 15 minutes, the lock was dried for 2 minuteswith a hairdryer.

The lock obtained was colored orange and the color obtained lasted forat least six shampooings.

Example 2

A composition was prepared comprising 10% by weight of pigment 2 in theabove-described coloring medium. The cyanoacrylate monomer was added tothis composition to give a final monomer concentration of 10% by weight.0.5 g of this composition was applied to a lock of clean, dry naturalhair with a tone height of 4, which had been wetted with 0.5 g of water.

After an exposure time of 15 minutes, the lock was dried for 2 minuteswith a hairdryer. A gold-colored lock was obtained.

The coloration thus obtained was highly resistant to shampooing.

Example 3 Methylheptyl Cyanoacrylate Monomer

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid40 g Prestige bronze brown iron oxide/mica nacre, Eckart 10 gMethylheptyl cyanoacrylate from Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 4 Methylheptyl Cyanoacrylate Monomer with Acetic Acid

The following composition A was produced: Methylheptyl cyanoacrylatefrom Chemence 97.5 g Glacial acetic acid  2.5 g

The following composition B was produced: DC 1501 Fluid 40 g DC 245Fluid 40 g Prestige bronze nacre, Eckart 10 g Composition A 10 g

0.5 g of composition B was applied to a lock of 1 g of clean, wet hair.After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 5 Ethylhexyl Cyanoacrylate Monomer

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid40 g Prestige bronze nacre, Eckart 10 g Ethylhexyl cyanoacrylate O-60from Tong Shen 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 6 Butyl Cyanoacrylate Monomer

The following composition I was produced: Butyl cyanoacrylate B-60 fromTong Shen 90 g Glacial acetic acid 10 g

The following composition J was produced: DC 1501 Fluid 40 g DC 245Fluid 40 g Prestige bronze nacre, Eckart 10 g Composition I 10 g

1.5 g of composition J was applied to a lock of 1 g of clean, wet hair.After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 7 Ethoxyethyl Cyanoacrylate Monomer

The following composition K was produced: DC 1501 Fluid 37.5 g DC 245Fluid 37.5 g Prestige bronze nacre, Eckart   10 g Glacial acetic acid  5 g Ethoxyethyl cyanoacrylate EO 460   10 g from Tong Shen

0.5 g of the composition K was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 8 Mixture of Methylheptyl Cyanoacrylate and EthylhexylCyanoacrylate Monomers

The following composition C was produced: Methylheptyl cyanoacrylatefrom Chemence 97.5 g Ethylhexyl cyanoacrylate O-60 from Tong Shen  2.5 g

The following composition D was produced: DC 1501 Fluid 40 g DC 245Fluid 40 g Prestige bronze nacre, Eckart 10 g Composition C 10 g

1.5 g of composition D was applied to a lock of 1 g of clean, wet hair.After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 9 Mixture of Methylheptyl Cyanoacrylate and Butyl CyanoacrylateMonomers

The following composition E was produced: Methylheptyl cyanoacrylatefrom Chemence 67.5 g Butyl cyanoacrylate B-60 from Tong Shen 27.5 gGlacial acetic acid   5 g

The following composition F was produced: DC 1501 Fluid 40 g DC 245Fluid 40 g Prestige bronze nacre, Eckart 10 g Composition E 10 g

1.5 g of composition F was applied to a lock of 1 g of clean, wet hair.After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 10 Titanium Oxide/Mica Nacre

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid40 g Prestige Gold titanium oxide/mica nacre, Eckart 10 g Methylheptylcyanoacrylate from Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 11 Iron Oxide-Titanium Oxide/Mica Nacre

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid40 g Prestige Sun Gold brown iron oxide-titanium 10 g oxide/mica nacre,Eckart Methylheptyl cyanoacrylate from Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 12 Iron Oxide/Synthetic Mica Nacre

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid40 g Sunshine super bronze brown iron 10 g oxide/synthetic mica(fluorophlogopite) nacre from Sun Chemical Methylheptyl cyanoacrylatefrom Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 13 Titanium Oxide/Synthetic Mica Nacre

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid40 g Sunshine super blue titanium 10 g oxide/synthetic mica(fluorophlogopite) nacre from Sun Chemical Methylheptyl cyanoacrylatefrom Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 14 Titanium Black Pigment

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid39.2 g Titanium Black pigment from Biosynthis 10 g Polyhydroxystearicacid dispersant, 0.8 g sold under the name Octacare DSP OL 300 by AveciaMethylheptyl cyanoacrylate from Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 15 Black Iron Oxide

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid39.2 g Natpure Black LC 9089 black iron oxide 10 g from SensientPolyhydroxystearic acid dispersant, 0.8 g sold under the name OctacareDSP OL 300 by Avecia Methylheptyl cyanoacrylate from Chemence 10 g

0.5 g of the composition was applied to a lock of 1 g of clean, wethair. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 16 Fluorescent Pigment

The following composition was produced: DC 1501 Fluid 40 g DC 245 Fluid39.2 g Sunbrite SG2516 Red orange fluorescent 10 g pigment from SunChemical Polyhydroxystearic acid dispersant, 0.8 g sold under the nameOctacare DSP OL 300 by Avecia Methylheptyl cyanoacrylate from Chemence10 g

0.5 g of the composition is applied to a lock of 1 g of clean, wet hair.After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored and the coloration obtained was resistant toshampoo.

Example 17 Quantum Dots

The following composition G was produced: DC 1501 Fluid 40 g DC 245Fluid 40 g Quantum Dots (CdSe—ZnS, emission 603 nm) 10 g sold by thecompany Evident Technologies Methylheptyl cyanoacrylate from Chemence 10g

1.5 g of composition G was applied to a lock of 1 g of clean, wet hair.After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored orange and the coloration obtained was resistant toshampoo.

Example 18 Quantum Dots as Pretreatment

The following composition H was produced: The following composition Hwas produced: Quantum Dots (CdSe—ZnS, emission 603 nm) 10 g sold by thecompany Evident Technologies The following composition I was produced:DC 1501 Fluid 45 g DC 245 Fluid 45 g Methylheptyl cyanoacrylate fromChemence 10 g

1 g of composition H was applied to a lock of 1 g of clean, wet hair.The lock was dried and then rewetted. 1 g of composition I was thenapplied. After an exposure time of 15 minutes, the lock was dried with ahairdryer for 2 minutes.

The lock was colored orange and the coloration obtained was resistant toshampoo.

1. A process for dyeing keratin materials comprising applying to thekeratin materials a dyeing composition comprising, in a suitable dyeingmedium, at least one pigment and at least one electrophiliccyanoacrylate monomer of formula (I)

in which R is chosen from alkyl radicals and alkoxyalkyl radicals. 2.The process according to claim 1, wherein the at least one electrophiliccyanoacrylate monomer is chosen such that in formula (I), the alkylradicals or alkoxyalkyl radicals of R comprise from 1 to 10 carbonatoms.
 3. The process according to claim 2, wherein in formula (I), thealkyl radicals or alkoxyalkyl radicals of R comprise from 6 to 10 carbonatoms.
 4. The process according to claim 3, wherein the at least oneelectrophilic cyanoacrylate monomer of formula (I) is chosen fromalkyl(C₆-C₁₀) cyanoacrylates.
 5. The process according to claim 1,wherein the at least one electrophilic cyanoacrylate monomer is ann-octyl 2-cyanoacrylate.
 6. The process according to claim 1, whereinthe at least one electrophilic cyanoacrylate monomer is present in anamount ranging from 0.1% to 80% by weight, relative to the total weightof the composition.
 7. The process according to claim 1, wherein the atleast one pigment is in the form of a pigment paste or powder.
 8. Theprocess according to claim 7, wherein the at least one pigment is chosenfrom inorganic pigments chosen from titanium dioxide, with or withoutsurface treatment, oxides of zirconium, oxides of cerium, oxides ofiron, oxides of chromium, manganese violet, ultramarine blue, chromiumhydrate and Prussian blue.
 9. The process according to claim 7, whereinthe at least one pigment is chosen from organic pigments chosen fromnitroso, nitro, azo, xanthene, quinoline, anthraquinone andphthalocyanine compounds, metal complex compounds, and isoindolinone,isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole,thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.10. The process according to claim 7, wherein the at least one pigmentis chosen from composite pigments composed of particles comprising aninorganic core, at least one binder attaching the organic pigments tothe core, and at least one organic pigment at least partly covering thecore.
 11. The process according to claim 7, wherein the at least onepigment is chosen from lakes comprising an inorganic substrate chosenfrom alumina, silica, calcium sodium borosilicate, calcium aluminiumborosilicate, and aluminium, on which a dye is adsorbed.
 12. The processaccording to claim 7, wherein the at least one pigment is chosen fromspecial-effect pigments chosen from nacreous pigments,interference-effect pigments not attached to a substrate, fluorescentpigments, phosphorescent pigments, photochromic pigments, thermochromicpigments and quantum dots.
 13. The process according to claim 12,wherein the at least one nacreous pigment is chosen from mica coatedwith titanium, mica coated with bismuth oxychloride, mica coated withtitanium and iron oxides, mica coated with titanium and Prussian blue orchromium oxide, nacreous pigments based on bismuth oxychloride, and micacoated with titanium and at least one organic pigment chosen fromnitroso, nitro, azo, xanthene, quinoline, anthraquinone andphthalocyanine compounds, metal complex compounds, and isoindolinone,isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole,thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.14. The process according to claim 11, wherein the at least oneinterference-effect pigment not attached to a substrate is chosen fromliquid crystals and holographic interference flakes.
 15. The processaccording to claim 1, wherein the at least one pigment is chosen fromcolored pigments.
 16. The process according to claim 1, wherein the atleast one pigment is present in the composition, in an amount for eachpigment, ranging from 0.05% to 50% by weight, relative to the totalweight of the composition.
 17. The process according to claim 16,wherein the at least one pigment is present in the composition, in anamount for each pigment, ranging from 0.1% to 35% by weight, relative tothe total weight of the composition.
 18. The process according to claim1, wherein the size of the at least one pigment ranges from 10 nm to 200μm.
 19. The process according to claim 1, wherein the composition isanhydrous.
 20. The process according to claim 1, wherein the suitabledyeing medium is chosen from aromatic alcohols, fatty alcohols, modifiedor non-modified polyols, volatile or non-volatile silicones, mineraloils, organic oils or vegetable oils, oxyethylenated ornon-oxyethylenated waxes, paraffins, alkanes, fatty acids, fatty amidesand fatty esters.
 21. The process according to claim 1, wherein thecomposition further comprises at least one nucleophile.
 22. The processaccording to claim 21, wherein the at least one nucleophile is water.23. The process according to claim 21, wherein at least one firstcomposition comprising the at least one pigment is applied to thekeratin materials, and at least one second composition comprising the atleast one electrophilic cyanoacrylate monomer of formula (I), is appliedto the keratin materials, wherein the at least one nucleophile ispresent in the at least one first composition comprising the pigment, orin a separate third composition.
 24. The process according to claim 23,wherein the at least one first composition comprising the at least onepigment is an aqueous pigment composition and the at least one secondcomposition comprising the at least one electrophilic cyanoacrylatemonomer of formula (I) is anhydrous.
 25. The process according to claim1, wherein the keratin materials are keratin fibers.
 26. A coloring kitcomprising at least one first composition comprising at least onepigment, at least one second composition comprising at least oneelectrophilic cyanoacrylate monomer of formula (I):

in which R is chosen from alkyl radicals and alkoxyalkyl radicals, andat least one third composition comprising at least one nucleophile. 27.The coloring kit according to claim 26, wherein the at least one firstcomposition comprising the at least one pigment and the at least onesecond composition comprising the at least electrophilic cyanoacrylatemonomer of formula (I) are present in the same anhydrous composition.28. A dyeing composition comprising, in a suitable dyeing medium, atleast one pigment in an amount greater than 5% by weight relative to thetotal weight of the composition, and at least one electrophiliccyanoacrylate monomer of formula (I):

in which R is chosen from alkyl radicals and alkoxyalkyl radicals.